CN101743287B - Coating composition with accelerated low temperature cure - Google Patents
Coating composition with accelerated low temperature cure Download PDFInfo
- Publication number
- CN101743287B CN101743287B CN200880024628.8A CN200880024628A CN101743287B CN 101743287 B CN101743287 B CN 101743287B CN 200880024628 A CN200880024628 A CN 200880024628A CN 101743287 B CN101743287 B CN 101743287B
- Authority
- CN
- China
- Prior art keywords
- coating composition
- methods
- composition
- methyl
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/12—Cellulose acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
Abstract
A coating composition including an unsaturated resin selected from polyesters, alkyds or combinations thereof; an alkoxy (meth)acrylic functional monomer, and a thermoplastic compound containing active hydrogen groups; a curing agent; and a curing promoter such as at least one metal drier.
Description
Technical field
The present invention relates to a kind of coating composition, this coating composition is for example suitable for preparation, for modifying colored paint, priming paint, sealing agent and the top coat of various base materials (timber, plastics and metal).
Background technology
Traditional industry protective coating based on urea/terpolycyantoamino-formaldehyde resin cross-linking system has good performance and cost benefit.Yet this coating is due to the during curing current welcome that is not too subject to human consumer of release formaldehyde.Alternative coatings chemistry product (such as isocyanic ester or the crosslinked system of ethylenimine) can solve health or safety problem, but conventionally have than the high raw materials cost of urea/formaldehyde resin system.Other alternative coatings chemistry product (such as epoxide or silane compound) are also very expensive, and conventionally must at relatively high temperature, solidify.And other alternative coatings chemistry product (such as comprising the curing unsaturated polyester coating system of cinnamic organo-peroxide) do not get consumer reception because health and safety reason is current yet.Containing the polyester coating system of cinnamic peroxide cure, conventionally do not need that solidification value is higher and/or set time is longer, this is not too suitable to many commercial applications.
Summary of the invention
Generally speaking, the present invention relates to the similar or better coating composition of the crosslinked coating system of a kind of condition of cure and raw materials cost and traditional urea/terpolycyantoamino-formaldehyde resin.This coating composition solidifies obviously variable color, and this makes them for example be very suitable for preparation, for modifying colored paint, priming paint, sealing agent and the top coat of various base materials (timber, plastics and metal).In a preferred embodiment, coating composition is at least substantially free of any one in formaldehyde, isocyanic ester and vinylbenzene.
On the one hand, content disclosed by the invention relates to a kind of coating composition, and it comprises unsaturated polyester, and described unsaturated polyester is selected from polyester, Synolac or its combination; Alkoxyl group (methyl) trifunctional acrylate monomer; The thermoplastic compound of containing reactive hydrogen base; Solidifying agent; And curing catalyst, such as at least one metal drier.
On the other hand, content disclosed by the invention relates to a kind of method of preparing coating composition, described method comprises makes following each component reaction to form coating composition: (1) first component A, it comprises the unsaturated polyester resin to about 90wt% with respect to the about 20wt% of gross weight of described composition, and about 1wt% is to alkoxyl group (methyl) the acrylic acid functionalized monomer of about 50wt% and the thermoplastic compound of containing reactive hydrogen base; With about 0.1wt% at least one metal drier to about 3wt%; (2) second component B, it comprises about 0.5wt% at least one organo-peroxide of about 5wt%.
On the other hand, content disclosed by the invention relates to a kind of method, described method comprises that (1) provides a kind of coating composition, and described coating composition comprises unsaturated polyester resin, alkoxyl group (methyl) acrylic acid functionalized monomer and contains the thermoplastic compound under solidifying of causing at free radical with reactive reactive hydrogen base; At least one metal drier and superoxide; (2) described coating composition is coated on base material.
On the other hand, content disclosed by the invention relates to a kind of base material that is coated with curing coating composition on it.Described coating composition comprises unsaturated polyester resin; The monomer of alkoxyl group (methyl) acrylic acid functionalized and contain the thermoplastic compound under solidifying of causing at free radical with reactive reactive hydrogen base; At least one metal drier and superoxide.
Details of one or more embodiments of the invention are set forth in following declaratives.Read following description and claim postscript, other features, objects and advantages of the present invention will be obvious.
Embodiment
In one embodiment, coating composition comprises at least one in unsaturated polyester resin, Synolac or its combination; The monomer of at least one alkoxyl group (methyl) acrylic acid functionalized and the thermoplastic compound of containing reactive hydrogen base; Solidifying agent and curing catalyst, such as metal drier.
Various unsaturated polyesters and Synolac all can be used in this coating composition.Can use any functionalized polyesters or Synolac with ethylene linkage unit (ethylenic unit).Unsaturated polyester and the Synolac with hydroxyl, carboxyl or allyl ethers functional group are suitable, preferably have unsaturated polyester resin and the Synolac of allyl ethers functional group.Preferred unsaturated polyester resin and Synolac have approximately 500 to approximately 10000, preferably approximately 1000 to approximately 6000, more preferably from about 2000 to approximately 5000 weight-average molecular weight.
Preferably use unsaturated polyester resin, suitable example includes but not limited to the AG from Bayer, Pittsburgh, those that PA obtains with trade(brand)name Roskydal, particularly preferably Roskydal502BA.
The consumption of unsaturated polyester is generally about 10wt% to about 80wt% with respect to the gross weight of coating composition, be preferably at least about 20wt% to about 60wt%, more preferably at least about 30wt% to about 50wt%.
Coating composition also comprises monomer and the thermoplastic compound of at least one alkoxyl group (methyl) acrylic acid functionalized.
The monomer of suitable alkoxyl group (methyl) acrylic acid functionalized comprises outstanding (methyl) acrylic-functional of (1) at least one side, and it is positioned at end and/or along skeleton; (2) at least one alkoxyl group (OR, wherein R is any alkyl group) spacer group, it is along skeleton.In this application, " (methyl) vinylformic acid " and symbol " Ac " refer to acrylate-based, methacrylate based or its mixed group and combination.
The monomer of preferred alkoxyl group (methyl) acrylic acid functionalized has approximately 200 to approximately 2000 molecular weight, and comprises a plurality of (methyl) acrylic-functional and at least one alkoxyl group along its main chain.Preferred alkoxyl group (methyl) acrylic acid functionalized monomer comprises two (methyl) acrylic acid functionalized and compounds three (methyl) acrylic acid functionalized, and its main chain has at least one alkoxyl group.Described alkoxyl group is preferably ethyleneoxy group or propylidene oxygen base.Most preferably, skeleton comprises approximately 8 to approximately 16, preferably approximately 8 to approximately 12, more preferably from about 8 oxyethyl groups or propoxy-repeating unit, particularly preferably oxyethyl group repeating unit.
For example, particularly preferred monomer can have formula [Ac-O-R
1-(OR
2)
n-R
1-O-Ac], wherein, R
1and R
2or the two can be (CH
2)
x, x=2, and n=8 to 12.
Suitable alkoxyl group (methyl) acrylic acid functionalized monomer includes but not limited to can be from SartomerCorp., Exton, the polyoxyethylene glycol that PA buys with trade(brand)name Sartomer SR 209,210,252,259,268,344,603,610,644,740 or polypropylene glycol two (methyl) acrylate and/or its combination.
The content of the monomer of alkoxyl group (methyl) acrylic acid functionalized is generally about 0.5wt% to about 50wt% with respect to the gross weight of coating composition, is preferably about 1wt% to about 30wt%, and more preferably about 3wt% is to about 10wt%.
Expectation replaces the organic group using in coating composition of the present invention.Therefore,, when term " group " is used to describe chemical substituting group, described chemical substance comprises that in unsubstituted group and chain, (in alkoxy base) has conventional substituent those groups of O, N, Si or S atom and carbonyl or other.For example; phrase " alkyl " not only comprises the hydrocarbon alkyl substituent that pure open chain is saturated; such as methyl, ethyl, propyl group, tertiary butyl etc., also comprise the alkyl substituent with other substituting group known in the art (such as hydroxyl, alkoxyl group, alkyl sulphonyl, halogen atom, cyano group, nitro, amino, carboxyl etc.).Therefore, " alkyl " comprises ether, haloalkyl, 4-nitro alkyl, carboxyalkyl, hydroxyalkyl, sulphonyl alkyl (sulfoalkyl) etc.
Coating composition also comprises the thermoplastic polymer with reactive hydrogen base except alkoxyl group (methyl) acrylic acid functionalized monomer, and this reactive hydrogen base causes at free radical has reactivity under solidifying.Suitable thermoplastic polymer comprises thermoplasticity secondary accelerator compound, and existing evidence proves that these thermoplasticity secondary accelerator compounds can promote curing reaction and can improve at least one character (such as sag prevention and snappiness) of uncured coating or solidified coating.This thermoplastic compound can comprise any synthetic resins with reactive hydrogen.Suitable example comprises cellulose base resin and acetyl oxygen or the functionalized vinylformic acid of acetic ester, and these can be obtained by the radical polymerization of olefinic type monomers.Preferred example includes, but not limited to the resin of Mierocrystalline cellulose or cellulose-derived, such as cellulose acetate butyric ester (CAB), cellulose acetate (CA) and combination thereof.
The content of thermoplastic compound in coating composition is generally about 20wt% at the most with respect to the gross weight of this coating composition, is preferably about 0.2wt% to about 20wt%, and more preferably about 0.5wt%, to about 10wt%, most preferably is about 0.5wt% to about 6wt%.
Coating composition also preferably comprises at least one solidifying agent.Can use various solidifying agent, particularly preferably superoxide, specifically organo-peroxide.The example of organo-peroxide comprises ketone peroxide, crosses ester, crosses acetal and benzoyl peroxide, such as by Arkema, and those that Philadelphia PA. obtains with trade(brand)name Luperox.Preferred ketone peroxide, suitable ketone peroxide is by Arkema, and Inc. provides with trade(brand)name Luperox and by Norac, Inc., Azusa, CA provides with trade(brand)name Norox.Norox MEKP-9 particularly preferably, it is the solution of ethyl methyl ketone (MEK) superoxide in dimethyl phthalate.
Solidifying agent is generally about 0.2wt% to about 5wt% at the content of coating composition with respect to the gross weight of this coating composition, is preferably about 0.5wt% to about 3wt%, and more preferably about 0.5wt% is to about 2.0wt%.
Coating composition also comprises at least one metal drier to improve curing speed.Suitable metal drier comprises organic acid metal-salt, and the unsaturated polyester that its effective catalysis is used in coating composition carries out radical polymerization.Metal drier is the metal-salt of ring-type alkanoic acid (such as naphthenic acid), alkanoic acid (such as neodecanoic acid) and C8 to C20 lipid acid normally.Suitable metal comprises Co, Mn, Pb, Ce, Zr, Ca, Zn, Bi, Cu, Cr, Li, K, Ni, Ne and composition thereof and combination.Preferred metal drier comprises the naphthenate of K, Co, Mg, Ca and C8 to C20 soap and composition thereof and combination.Particularly preferred metal drier comprises Co salt, for example, comprise cobalt naphthenate, citric acid cobalt, Acetyl Acetone acid cobalt, 2 ethyl hexanoic acid ketone cobalt etc.In coating composition, preferably use the metal drier in organic hydrocarbon solvent.Suitable commercial metal siccative comprises from Tenneco, Inc., Piscataway, those that NJ obtains with trade(brand)name Syn Nuxtra Co 12, SynNuxtra Mg 12 and Syn Nuxtra K 15.
Metal drier can be present in coating composition with any catalytically effective amount, conventionally the consumption of siccative is that about 0.1wt% is to about 2wt% with respect to the gross weight of this coating composition, be preferably about 0.2wt% to about 2wt%, more preferably about 0.3wt% is to about 1.5wt%.
Coating composition is preferably solvent-borne coating composition.Suitable organic solvent includes but not limited to butylacetate, ethyl methyl ketone (MEK), dimethylbenzene and composition thereof and combination.
The consumption of organic solvent in coating composition is preferably about 5wt% to about 80wt% with respect to the gross weight of this coating composition, is preferably about 5wt% to about 70wt%, and more preferably about 5wt% is to about 60wt%.
Alternatively, the monomer of extra (methyl) acrylic acid functionalized can be mixed to coating composition to improve and/or to revise the character of solidified coating.Suitable (methyl) acrylic acid functionalized monomer preferably comprises a plurality of (methyl) acrylate-functional groups, and these functional groups can be positioned at the end of monomer and/or along the skeleton of monomer.
In one embodiment, optional (methyl) acrylic acid functionalized monomer includes but not limited to have two (methyl) acrylate of formula Ac-(Z) n-Ac, and wherein z is preferably alkoxyl group, and n is 1 to 5.In another embodiment, (methyl) acrylic acid functionalized compound includes but not limited to have formula Ac-[Z (Ac)
2]
nthree (methyl) acrylate, Z alkoxyl group preferably wherein, n is 1 to 8.Alkoxy base Z in two (methyl) acrylic compound and three (methyl) acrylic compound can comprise straight chained alkyl group or branched alkyl group, and these alkyl groups can be substituted or not be substituted.Preferably be unsubstituted, there is the linear alkyl group that is less than approximately 5 carbon atoms.
Suitable example comprises that tripropylene glycol diacrylate is (such as by Sartomer Corp., Exton, those that PA provides with trade(brand)name Sartomer SR 306) and Viscoat 295 (such as by Sartomer Corp., Exton, those that PA provides with trade(brand)name Sartomer SR 351) and combination.
The consumption of this acrylic acid functionalized monomer in coating composition is generally about 0wt% to about 50wt% with respect to the gross weight of this coating composition, is preferably about 2wt% to about 20wt%, and more preferably about 2wt% is to about 10wt%.
Optional at least one tensio-active agent that also comprises of coating composition is to strengthen flowing/homogenizing character and/or wetting property of coating composition.Suitable tensio-active agent includes but not limited to silicone and polyacrylic ester, such as by Byk-Chemie, and Wesel, those that Germany provides with trade(brand)name BYK.Suitable compound comprises Byk 333, Byk 348, Byk 353, Byk 380 and composition thereof and combination.
The content of tensio-active agent (if existence) in coating composition is extremely about 3wt% of about 0.1wt% with respect to the gross weight of this coating composition, is preferably about 0.1wt% to about 2wt%, and more preferably about 0.1wt% is to about 1wt%.
Optional at least one rheology control agent that also comprises of coating composition is to control this coating composition sagging (sagging) and pigment sedimentation.Suitable rheology control reagent includes but not limited to polyureas, such as by Byk-Chemie, and Wesel, those that Germany provides with trade(brand)name BYK.Suitable compound comprises Byk 410,411 and composition thereof and combination.
The content of rheology control agent (if existence) in coating composition is extremely about 3wt% of about 0.1wt% with respect to the gross weight of this coating composition, is preferably about 0.1wt% to about 2wt%, and more preferably about 0.1wt% is to about 1wt%.
The optional solid particulate that also comprises of coating composition, such as pigment, filler, releasing agent, tinting material, wax etc.Preferably use pigment to make coating composition dry and there is needed covering property and opacity when curing.Except tinting material, can also use pigment to make base material there is required color, for example white pigment can be used to form white coating composition.Can with such as the flatting agent of silica, replace or with required color cooperation, thereby make base material there is required sub-light finish coat (matte finish).In the present invention, opacity, modification texture and/or aesthetic feeling that the consumption of suitable solid particulate is enough to that substrate to be coated is had makes us hope.Suitable pigment comprises aluminum oxide, titanium oxide, zinc oxide etc.The example that can be used on the pigment in coating composition described herein comprises can derive from E.I.duPont de Nemours of Wilmington, the Ti-Pure R-900 of Del; Suitable flatting agent comprises for example unformed silica (silicon oxide), such as can be from Baltimore, and those that the W.R.Grace Company of Md obtains with trade(brand)name Syloid 169.Suitable filler comprises for example clay, talcum or other mineral compound.The example that can be used on the filler in coating composition described herein comprises the Minex 10 that can derive from Unimin Specialty Minerals Inc.
The consumption of solid particulate in coating composition can change in wide region, and this depends on final modification application.For example, the consumption of solid particulate is preferably less than the approximately 40wt% of coating composition.
At least one metal drier and the arbitrarily optional additive of the acid-functionalized monomer of unsaturated polyester, alkoxy propone and thermoplastic compound, solidifying agent, catalytically effective amount can be blended in organic solvent, thereby form coating composition.Preferably, the second component that is called as in this article the first component of component A and is called as in this article B component is mixed, thereby form coating composition.For example, component A (preferred solvent type) can comprise unsaturated polyester, alkoxyl group (methyl) acrylic acid functionalized monomer and thermoplastic compound, metal drier and arbitrarily optional additive.B component comprises solidifying agent.
Coating composition can be formulated into colored paint, priming paint, sealing agent, top coat etc. to modify timber, Engineered Wood Product Manufacturing, plastics and metal base.Because this coating composition is fast setting at low temperatures, so be particularly suitable for being applied on wood substrate, typically used comprises furniture and/or office furniture, cabinet, floor, window frame, door-plate, doorframe etc.
Can coating composition be coated on base material by any ordinary method (for example comprise spray, brushing, dip-coating, sheet are coated with, volume is coated with (coil coating), roller coat etc.).The injection system that discovery contains two-pack injection rifle (with equalizer) can provide consistent especially result.
After coating, thereby being solidified, coating composition on base material, forms protective coating and/or decorative paint.Can change set time, and this depends on selected condition of cure, such as temperature, retention time, room temperature etc.If need, can for example heat substrate to be coated in conventional baking oven.Although do not wish to be entangled in any theory, but the data obtained shows at present, the monomer of (methyl) acrylic acid functionalized or there is the alkoxyl group linking group that free radical is had in the thermoplastic resin of reactive reactive hydrogen base and can strengthen the curing reaction of unsaturated polyester compound and promote film forming, thus shortened set time at low temperatures and obtained low discoloration coating.
Then, coating composition can solidify (referring in this application the temperature lower than 70 ℃) at low temperatures, thereby on base material, forms coating.At room temperature, coating composition solidifies being less than in approximately 24 hours.Under the solidification value of preferred approximately 30 ℃ to approximately 60 ℃, coating composition is being less than in approximately 30 minutes, is more preferably being less than in approximately 20 minutes and is solidifying.Under the solidification value of approximately 30 ℃ to approximately 60 ℃, coating composition is in approximately 5 minutes to approximately 30 minutes, more preferably in approximately 5 minutes to approximately 20 minutes, even more preferably solidified in approximately 6 minutes to approximately 15 minutes.
In some embodiments, coating composition and coating are substantially free of formaldehyde, isocyanic ester and vinylbenzene.In a preferred embodiment, coating composition and coating be not substantially containing formaldehyde, isocyanic ester and vinylbenzene, more preferably substantially completely not containing formaldehyde, isocyanic ester and vinylbenzene, most preferably completely not containing formaldehyde, isocyanic ester and vinylbenzene.
Term " is substantially free of " and refers to, coating composition and coating have or solidify after discharge any one in formaldehyde, isocyanic ester and the vinylbenzene that is no more than approximately 0.5 % by weight.Term " substantially containing " refers to, coating composition and coating have or solidify after discharge any one in formaldehyde, isocyanic ester and the vinylbenzene that is no more than 0.5 % by weight.Term " substantially completely containing " refers to, coating composition and coating have or solidify after discharge any one in formaldehyde, isocyanic ester and the vinylbenzene that is no more than 0.1 % by weight.Term " completely containing " refers to, coating composition and coating have or solidify after discharge any one in formaldehyde, isocyanic ester and the vinylbenzene that is less than 5/1000000ths parts (ppm).
In a preferred embodiment, the coating after solidifying on base material is substantially colourless, in a preferred embodiment, forms substantially colourless film.In some embodiments, solidified coating forms water-white, colorless film.The color of sample can be by any known technology based on CIE L
*a
*b
*color space (color scheme) is evaluated.For example, for the color of assess sample, can use spectrophotometer, such as by Datacolor Inc with trade(brand)name Spectraflash, those that Model No.SF650X provides.
Curing coating or highly flexible, this has guaranteed, and it can not break from base material (especially edge or complex outline), cracked or layering.The snappiness that adopts RentagonMandrel Rods testing coating according to ASTM D522-80, result is divided into 1 to 10 grade, and wherein 10 represent the most pliable and the toughest coating, and 1 represents the coating of snappiness minimum.
embodiment
In 2000ml stainless steel wide-mouth beaker, prepare 1000 grams of various coating product for test.The first component A is according to table 1 preparation, each composition under stirring (10-15RPM), it progressively being added in wide-mouth beaker of accurately weighing.In table 1, composition 6-7 illustrates preferred coating composition, and composition C1-C2 represents comparative example.
After obtaining completely uniformly preparation, filter (10micro filter bag) each sample and be stored in the metal tin of lining for test.97 grams of each component A that weigh add in the metal tin (250ml) of lining, then under agitation drip 3 grams of B component.Adopt the bird type coating device of 3 mils to draw painting biased sample on white Leneta Charts, and will be coated with at room temperature air rapid drying of Leneta Charts 15 minutes, then Leneta Charts is placed in the baking oven of 50 ℃ and solidifies.At coatingsurface, not after the finger of slimy milk Rubber gloves, record set time.
Utilize the Spectraflash SF650X instrument of Datacolor (Lawrenceville, NJ) to measure the color readings of curing coating composition on white Lenenta Charts with respect to color standard white background.Utilize Pentagon Mandrel Rods according to ASTM D522-80, at room temperature to measure the snappiness of the coating composition that is cured, result is divided into 1 to 10 grade, and wherein 10 represent the most pliable and the toughest coating, and 1 represents the coating of snappiness minimum.The character of gained coating composition is listed in table 2.
Table 1 coating composition
The character of table 2 coating composition
| Formula | Set time (min) | Color, dE | Snappiness ＊ |
| Formula C1 | 28 | 4.12 | 5 |
| Formula C2 | 20 | 7.18 | 3 |
| Formula 1 | 23 | 3.88 | 7 |
| Formula 2 | 24 | 3.88 | 7 |
| Formula 3 | 28 | 3.91 | 5 |
| Formula 4 | 25 | 4.22 | 6 |
| Formula 5 | 27 | 4.31 | 5 |
| Formula 6 | 19 | 4.08 | 7 |
| Formula 7 | 17 | 4.16 | 8 |
C1 compares with reference examples, and the composition 6 and 7 that adds polyethyleneglycol diacrylate has obviously the snappiness of solidification rate faster and shorter set time, colour-change still less and improvement.
Adding more metal drier has accelerated solidifying of coating product and has shortened set time (composition C2).Yet, use more metal drier to make variable color obvious, from attractive in appearance, this is not so good, especially not so good in light color or white substrate.
The polyacrylic acid Paralloid B66 (example 5) that contains non-reactive hydrogen with interpolation compares with reference composition C1, adds cellulose acetate butyric ester (CAB) and strengthened curing reaction in example 4,6 and 7.
The two composition all adding of polyethylene glycol acrylate and cellulose acetate butyric ester (composition 6 and 7) compare with composition C2 there is the fastest curing speed, good snappiness and low discoloration.
Various embodiment of the present invention has been described.These embodiments and other embodiment are all within the scope of the appended claims.
Claims (29)
1. a coating composition, it comprises:
Unsaturated polyester resin, wherein said unsaturated polyester resin has allyl ethers functional group;
The monomer of alkoxyl group (methyl) acrylic acid functionalized, the monomer of described alkoxyl group (methyl) acrylic acid functionalized is selected from the compound of two and three (methyl) acrylic acid functionalized on skeleton with 8-16 oxyethyl group or propoxy-group;
The thermoplastic compound of containing reactive hydrogen base, wherein said thermoplastic compound is selected from cellulose acetate butyric ester (CAB), cellulose acetate (CA) and combination thereof;
At least one metal drier, wherein said metal drier is organic acid metal-salt, and wherein said metal comprises Co, Mn, Pb, Ce, Zr, Ca, Zn, Bi, Cu, Cr, Li, K, Ni, Ne, Mg and composition thereof and combination; With
Solidifying agent; Wherein said composition have or solidify after discharge any one in formaldehyde, isocyanic ester and the vinylbenzene that is no more than 0.5 % by weight.
2. coating composition as claimed in claim 1, wherein, described alkoxy base is oxyethyl group.
3. coating composition as claimed in claim 1, wherein, the monomer of described alkoxyl group (methyl) acrylic acid functionalized comprises at least one in ethylene glycol unit and propylene glycol unit.
4. coating composition as claimed in claim 3, wherein, the described skeleton of the monomer of described alkoxyl group (methyl) acrylic acid functionalized comprises 8-12 oxyethyl group or propoxy-group.
5. coating composition as claimed in claim 3, wherein, the described skeleton of the monomer of described alkoxyl group (methyl) acrylic acid functionalized comprises 8 oxyethyl groups or propoxy-group.
6. composition as claimed in claim 1, wherein, described metal comprises K, Co, Mg and composition thereof and combination.
7. composition as claimed in claim 1, wherein, described metal comprises Co.
8. composition as claimed in claim 1, wherein, described organic acid comprises C8 to C20 lipid acid.
9. composition as claimed in claim 1, also comprises second (methyl) trifunctional acrylate monomer.
10. composition as claimed in claim 1, at least one in also comprises surfactant, filler, pigment and tinting material.
11. compositions as claimed in claim 1, wherein, described solidifying agent comprises at least one peroxide compound.
12. compositions as claimed in claim 11, wherein, described superoxide is ketone peroxide.
13. 1 kinds of methods of preparing coating composition, described method comprises: thereby make following each component reaction form coating composition:
(1) first component A, it comprises:
With respect to the unsaturated polyester resin of the gross weight 20wt% to 90wt% of described coating composition, wherein, described unsaturated polyester resin comprises allyl ethers functional group;
The alkoxyl group of 1wt% to 50wt% (methyl) acrylic acid functionalized monomer and the thermoplastic compound of containing reactive hydrogen, wherein said alkoxyl group (methyl) acrylic acid functionalized monomer is selected from the compound of two and three (methyl) acrylic acid functionalized on skeleton with 8-16 oxyethyl group or propoxy-group, and wherein said thermoplastic compound is selected from the resin of celluosic resin and cellulose-derived; With
At least one metal drier of 0.1wt% to 3wt%, wherein said metal drier is organic acid metal-salt, and wherein said metal comprises Co, Mn, Pb, Ce, Zr, Ca, Zn, Bi, Cu, Cr, Li, K, Ni, Ne, Mg and composition thereof and combination; With
(2) second component B, at least one organo-peroxide that it comprises 0.5wt% to 5wt%, wherein said coating composition have or solidify after discharge any one in formaldehyde, isocyanic ester and the vinylbenzene that is no more than 0.5 % by weight.
14. methods as claimed in claim 13, wherein, at least one organic solvent that component A also comprises 5wt% to 80wt%.
15. methods as claimed in claim 13, wherein, component A also comprises the monomer of at least one second (methyl) acrylic acid functionalized of 50wt% at the most.
16. methods as claimed in claim 13, wherein, described metal comprises K, Co, Mg and composition thereof and combination.
17. methods as claimed in claim 13, wherein, described metal comprises Co.
18. methods as claimed in claim 13, wherein, described coating composition also comprises the described thermoplastic compound of 0.2wt% to 20wt%.
19. methods as claimed in claim 13, wherein, described thermoplastic compound is selected from cellulose acetate butyric ester (CAB) and cellulose acetate and combination thereof.
20. methods as claimed in claim 13, wherein, described thermoplastic compound is cellulose acetate butyric ester (CAB).
21. methods as claimed in claim 13, wherein, at least one tensio-active agent that described coating composition also comprises 0.1wt% to 3wt%.
22. 1 kinds of methods that form solidified coating on base material, it comprises
The coating composition of claim 1 is coated on base material.
23. methods as claimed in claim 22, also comprise the step of solidifying described coating composition, thereby form solidified coating.
24. methods as claimed in claim 23, wherein, described coating composition is at room temperature less than in 24 hours and solidifies.
25. methods as claimed in claim 23, wherein, described coating composition solidified at the temperature of 30 ℃ to 60 ℃ in 30 minutes to 60 minutes.
26. methods as claimed in claim 23, wherein, described coating composition is being less than in 20 minutes and is solidifying at the temperature of 50 ℃ to 60 ℃.
27. methods as claimed in claim 22, wherein, described coating composition applies by injection.
28. methods as claimed in claim 27, wherein, described coating composition is by spraying to apply with bi-component spray gun system.
29. 1 kinds of base materials that are coated with the coating composition of the claim 1 that is cured on it, wherein, described in the coating composition that is cured have or solidify after discharge any one in formaldehyde, isocyanic ester and the vinylbenzene that is no more than 0.5 % by weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/879,021 | 2007-07-13 | ||
| US11/879,021 US7951856B2 (en) | 2007-07-13 | 2007-07-13 | Coating composition with accelerated low temperature cure |
| PCT/US2008/008472 WO2009011784A1 (en) | 2007-07-13 | 2008-07-10 | Coating composition with accelerated low temperature cure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101743287A CN101743287A (en) | 2010-06-16 |
| CN101743287B true CN101743287B (en) | 2014-02-19 |
Family
ID=39864803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880024628.8A Active CN101743287B (en) | 2007-07-13 | 2008-07-10 | Coating composition with accelerated low temperature cure |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US7951856B2 (en) |
| CN (1) | CN101743287B (en) |
| CA (1) | CA2693792C (en) |
| WO (1) | WO2009011784A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7951856B2 (en) * | 2007-07-13 | 2011-05-31 | Valspar Sourcing, Inc. | Coating composition with accelerated low temperature cure |
| EP2440625A1 (en) * | 2009-06-10 | 2012-04-18 | Basf Se | Use of radiation-curable coating compound to coat wood materials |
| CN101857790A (en) * | 2010-06-08 | 2010-10-13 | 武汉市科达云石护理材料有限公司 | Special color stone grout |
| US8974900B2 (en) * | 2011-05-23 | 2015-03-10 | Carestream Health, Inc. | Transparent conductive film with hardcoat layer |
| DK2744840T3 (en) * | 2011-08-19 | 2017-05-01 | Ppg Europe B V | Coating composition and application thereof |
| US20150197667A1 (en) * | 2014-01-15 | 2015-07-16 | Ppg Industries Ohio, Inc. | Polyester polymers comprising lignin |
| CN103980768B (en) * | 2014-05-16 | 2016-03-16 | 吴江市英力达塑料包装有限公司 | A kind of environment-friendlyfireproof fireproof paint and preparation method thereof |
| CN105295681A (en) * | 2014-06-29 | 2016-02-03 | 江苏飞翔涂料实业总公司 | Fast drying paint |
| BR112017012180B8 (en) | 2014-12-09 | 2022-05-10 | Arkema Inc | Compositions and methods for crosslinking polymers in the presence of atmospheric oxygen |
| CN107141982B (en) * | 2017-06-30 | 2019-10-18 | 嘉宝莉化工集团股份有限公司 | A kind of solvent-free, ordor removing unsaturated polyester woodwork coating and preparation method thereof |
| CN112063274B (en) * | 2020-08-06 | 2022-03-22 | 中华制漆(新丰）有限公司 | Unsaturated polyester primer and preparation method thereof |
| CN112341913A (en) * | 2020-11-30 | 2021-02-09 | 上海嘉宝莉涂料有限公司 | Unsaturated polyester resin coating and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2498091A (en) * | 1947-06-14 | 1950-02-21 | Du Pont | Cellulose nitrate coating compositions |
| US6126699A (en) * | 1999-06-29 | 2000-10-03 | Mccurley; Avery Lee | Sublimation printing of wooden articles |
| CN1273991A (en) * | 1999-05-12 | 2000-11-22 | 三有制漆株式会社 | Method of solidifying priming paint |
| JP2001172307A (en) * | 1999-12-20 | 2001-06-26 | Hitachi Kasei Polymer Co Ltd | Photocurable resin composition |
| CN1616514A (en) * | 2004-09-24 | 2005-05-18 | 中山大学 | Allyl ether modified polyurethane acrylate and its use |
| JP2006257370A (en) * | 2005-03-18 | 2006-09-28 | Ube Machinery Corporation Ltd | Composition for in-mold coating and method for producing in-mold coated molded product |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2955949A (en) | 1958-09-17 | 1960-10-11 | Exxon Research Engineering Co | Paint driers |
| JPS6254716A (en) * | 1985-09-04 | 1987-03-10 | Nippon Synthetic Chem Ind Co Ltd:The | Air-drying resin composition |
| US5539032A (en) * | 1994-03-07 | 1996-07-23 | The United States Of America As Represented By The Secretary Of The Navy | Corrosion resistant self-priming alkyd topcoats |
| US6518338B2 (en) * | 2001-05-08 | 2003-02-11 | Basf Corporation | Fast drying alkyd basecoat refinish composition |
| DE102004034646A1 (en) * | 2004-07-16 | 2006-02-16 | Basf Ag | Method for accelerating the wetting in paints |
| US7951856B2 (en) | 2007-07-13 | 2011-05-31 | Valspar Sourcing, Inc. | Coating composition with accelerated low temperature cure |
-
2007
- 2007-07-13 US US11/879,021 patent/US7951856B2/en active Active
-
2008
- 2008-07-10 WO PCT/US2008/008472 patent/WO2009011784A1/en active Application Filing
- 2008-07-10 CN CN200880024628.8A patent/CN101743287B/en active Active
- 2008-07-10 CA CA2693792A patent/CA2693792C/en active Active
-
2011
- 2011-04-21 US US13/091,891 patent/US8198348B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2498091A (en) * | 1947-06-14 | 1950-02-21 | Du Pont | Cellulose nitrate coating compositions |
| CN1273991A (en) * | 1999-05-12 | 2000-11-22 | 三有制漆株式会社 | Method of solidifying priming paint |
| US6126699A (en) * | 1999-06-29 | 2000-10-03 | Mccurley; Avery Lee | Sublimation printing of wooden articles |
| JP2001172307A (en) * | 1999-12-20 | 2001-06-26 | Hitachi Kasei Polymer Co Ltd | Photocurable resin composition |
| CN1616514A (en) * | 2004-09-24 | 2005-05-18 | 中山大学 | Allyl ether modified polyurethane acrylate and its use |
| JP2006257370A (en) * | 2005-03-18 | 2006-09-28 | Ube Machinery Corporation Ltd | Composition for in-mold coating and method for producing in-mold coated molded product |
Also Published As
| Publication number | Publication date |
|---|---|
| US8198348B2 (en) | 2012-06-12 |
| US20110201740A1 (en) | 2011-08-18 |
| WO2009011784A1 (en) | 2009-01-22 |
| US7951856B2 (en) | 2011-05-31 |
| CA2693792A1 (en) | 2009-01-22 |
| CN101743287A (en) | 2010-06-16 |
| CA2693792C (en) | 2013-09-03 |
| US20090017215A1 (en) | 2009-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101743287B (en) | Coating composition with accelerated low temperature cure | |
| CA1335909C (en) | Automotive coating compositions | |
| CN101712844B (en) | Composition for hard coat and molded product provided with hard coat layer | |
| EP2556107A1 (en) | Crosslinkable composition crosslinkable with a latent base catalyst | |
| WO1995035336A1 (en) | Thermosetting composition and method of forming topcoating film | |
| US10358573B2 (en) | Refinish coating composition | |
| US4495322A (en) | Silicone resin coating agent | |
| US3822232A (en) | Cold-setting coating composition based on carboxyl-containing vinyl polymer | |
| CN107446483B (en) | Ultraviolet light/moisture dual cure resin and its preparation method and application | |
| JPWO2021006290A1 (en) | Curable resin composition, cured film, coated resin molded body and multilayer film | |
| US6048617A (en) | Surface-coated molded plastic articles having good durability | |
| EP1772502A1 (en) | Oxidatively drying composition to be employed in thin layers comprising 1,2 dioxo compounds | |
| KR101176111B1 (en) | The process for preparing high polymerized urushiol from natural lacquer and industrial lacquer-gold paintscoating materials | |
| KR102121813B1 (en) | Coating composition | |
| CN111154373A (en) | Resin modified environment-friendly UV coating and preparation method thereof | |
| US3058934A (en) | Coating compositions containing z-vinyl- | |
| JPH01123817A (en) | Curable composition | |
| EP3810723B1 (en) | Coating composition | |
| JPH0841166A (en) | Resin composition and method for forming coating film | |
| CN117603487A (en) | High-hardness bio-based nylon film and preparation method thereof | |
| KR101846441B1 (en) | One-component type matt solvent paint composition for automotive top coating | |
| CN109504245A (en) | A kind of UV rosin modified phenolic resin car light vapor deposition base oil and preparation method thereof | |
| JP3274156B2 (en) | Paint composition using oxidation-curable fatty acid-modified vinyl resin | |
| JPS58173134A (en) | Painting of plastic | |
| JPH05132650A (en) | Low temperature-setting coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190203 Address after: Ohio, USA Patentee after: Xuanwei Investment Management Co.,Ltd. Address before: Ohio, USA Patentee before: Xuanwei Headquarters Co. Effective date of registration: 20190203 Address after: Ohio, USA Patentee after: Xuanwei Headquarters Co. Address before: Ohio, USA Patentee before: THE SHERWIN WILLIAMS Co. Effective date of registration: 20190203 Address after: Ohio, USA Patentee after: THE SHERWIN WILLIAMS Co. Address before: Ohio, USA Patentee before: Valspar Corp. Effective date of registration: 20190203 Address after: Ohio, USA Patentee after: Valspar Corp. Address before: Ohio, USA Patentee before: Industrial solution Co. Effective date of registration: 20190203 Address after: Ohio, USA Patentee after: Industrial solution Co. Address before: American Minnesota Patentee before: VALSPAR SOURCING, Inc. |
|
| TR01 | Transfer of patent right |